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Development of direct nucleophilic addition to inert amides

Research Project

Project/Area Number 24750045
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Organic chemistry
Research InstitutionKeio University

Principal Investigator

SATO TAKAAKI  慶應義塾大学, 理工学部, 講師 (70509926)

Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2013: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords有機化学 / 有機反応化学 / 天然物化学 / アミド / 求核付加反応 / 官能基選択性 / ジルコニウム / 全合成 / ステモナアルカロイド / ステモアミド
Outline of Final Research Achievements

Amide functional groups are found in a wide variety of organic molecules including pharmaceuticals and functional materials. Therefore, efficient synthesis of amide bonds has been extensively studied. On the other hand, transformation of the generated amide groups is less explored than their construction.
In this study, we developed direct nucleophilic addition to amide groups using unique properties of a zirconium reagent. The developed method enabled installation of two functional groups in a single reaction. The most conspicuous feature of our method is the high chemoselectivity. The reaction proceeded in the presence of a variety of sensitive functional groups such as esters. The reaction was successfully applied to the total syntheses of biologically active alkaloids.

Report

(4 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • 2012 Research-status Report
  • Research Products

    (45 results)

All 2015 2014 2013 2012 Other

All Journal Article (14 results) (of which Peer Reviewed: 14 results,  Acknowledgement Compliant: 5 results) Presentation (29 results) (of which Invited: 7 results) Book (1 results) Remarks (1 results)

  • [Journal Article] Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin2015

    • Author(s)
      Shirokane, K.; Tanaka, Y.; Yoritate, M.; Takayama, N.; Sato T.; Chida, N.
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 88 Issue: 4 Pages: 522-537

    • DOI

      10.1246/bcsj.20140398

    • NAID

      130005064992

    • ISSN
      0009-2673, 1348-0634
    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Iridium-Catalyzed Chemoselective Reductive Nucleophilic Addition to N-Methoxyamides2015

    • Author(s)
      Nakajima, M.; Sato T.; Chida, N.
    • Journal Title

      Org. Lett.

      Volume: 17 Issue: 7 Pages: 1696-1699

    • DOI

      10.1021/acs.orglett.5b00664

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Total Synthesis of Sphingofungin F by Orthoamide-Type Overman Rearrangement of an Unsaturated Ester2015

    • Author(s)
      Tsuzaki, S.; Usui, S.; Oishi, H.; Yasushima, D.; Fukuyasu, T.; Oishi, T.; Sato T.; Chida, N.
    • Journal Title

      Org. Lett.

      Volume: 17 Issue: 7 Pages: 1704-1707

    • DOI

      10.1021/acs.orglett.5b00475

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Two-step Synthesis of Multi-substituted Amines Using N-Methoxy Group as a Reactivity Control Element2014

    • Author(s)
      Yoritate, M.; Meguro, T.; Matsuo, N.; Shirokane, K.; Sato, T.; Chida, N.
    • Journal Title

      Chem. - Eur. J.

      Volume: 20 Issue: 26 Pages: 8210-8216

    • DOI

      10.1002/chem.201402231

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] (5R*)-5-[(2S*,5S*)-1-Meth¬oxy-5-phenyl¬pyrrolidin-2-yl]- 3-methyl¬furan-2(5H)-one2014

    • Author(s)
      Oishi, T.; Yoritate, M.; Sato, T.; Chida, N.
    • Journal Title

      Acta Cryst.

      Volume: E70 Issue: 8 Pages: o839-o839

    • DOI

      10.1107/s1600536814014974

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chemoselective Reductive Nucleophilic Addition to tertiary Amides, secondary Amides and N-Methoxyamides2014

    • Author(s)
      Nakajima, M.; Oda, Y.; Wada, T.; Minamikawa, R.; Shirokane, K.; Sato, T.; Chida, N.
    • Journal Title

      Chem. - Eur. J.

      Volume: 20 Issue: 52 Pages: 17565-17571

    • DOI

      10.1002/chem.201404648

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Nucleophilic Addition to N-Alkoxyamides2014

    • Author(s)
      Sato, T.; Chida, N.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 12 Issue: 20 Pages: 3147-3150

    • DOI

      10.1039/c4ob00389f

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Total Synthesis of (±)-Gephyrotoxin via Amide-Selective Reductive Nucleophilic Addition2014

    • Author(s)
      Shirokane, K.; Wada, T.; Yoritate, M.; Minamikawa, R.; Takayama, N.; Sato T.; Chida, N.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 53 Issue: 2 Pages: 512-516

    • DOI

      10.1002/anie.201308905

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] The Cascade- and Orthoamide-type Overman Rearrangements of Allylic Vicinal Diols2013

    • Author(s)
      Nakayama, Y.; Sekiya, R.; Oishi, H.; Hama, N.; Yamazaki, M.; Sato, T.; Chida, N.
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Issue: 36 Pages: 12052-12058

    • DOI

      10.1002/chem.201301216

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of (-)-Morphine: Application of Sequential Claisen/Claisen Rearrangement of an Allylic Vicinal Diol2013

    • Author(s)
      市來政人
    • Journal Title

      Chemistry An European Journal

      Volume: 19 Issue: 1 Pages: 264-269

    • DOI

      10.1002/chem.201203284

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Direct Nucleophilic Addition to N-Alkoxyamides2013

    • Author(s)
      Yanagita, Y. ; Nakamura, H. ; Shirokane, K. ; Kurosaki, Y. ; Sato, T. ; Chida, N.
    • Journal Title

      CHEMISTRY A EUROPEAN JOURNAL

      Volume: 19 Issue: 2 Pages: 678-684

    • DOI

      10.1002/chem.201202639

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Direct Chemoselective Allylation of Inert Amide Carbonyls2012

    • Author(s)
      Yukiko Oda
    • Journal Title

      Organic Letters

      Volume: 14 Issue: 3 Pages: 950-953

    • DOI

      10.1021/ol3000316

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Concise Synthesis of α-Trisubstituted Amines from Ketones Using N-Methoxyamines2012

    • Author(s)
      黒崎友介
    • Journal Title

      Organic Letters

      Volume: 14 Issue: 8 Pages: 2098-2101

    • DOI

      10.1021/ol300622r

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chirality Transfers via Sequential Sigmatropic Rearrangements of Allylic Vicinal Diols: Development and Application to Total Synthesis of (–)-Kainic Acid2012

    • Author(s)
      北元克典
    • Journal Title

      Eurpoean Journal of Organic Chemistry

      Volume: なし Issue: 22 Pages: 4217-4231

    • DOI

      10.1002/ejoc.201200523

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Presentation] 多段階合成を指向したN-メトキシアミンによる求電子的アミノ化反応の開発2015

    • Author(s)
      ○深見祐太朗、目黒達彦、和田崇正、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス/薬学部 (千葉県船橋市)
    • Year and Date
      2015-03-27
    • Related Report
      2014 Annual Research Report
  • [Presentation] 三級アミド、二級アミド、N-アルコキシアミド基に対する官能基選択的な求核付加反応の開発2015

    • Author(s)
      ○中島実奈美、小田友紀子、和田崇正、南川亮、白兼研史、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス/薬学部 (千葉県船橋市)
    • Year and Date
      2015-03-27
    • Related Report
      2014 Annual Research Report
  • [Presentation] レパジホルミンAの合成研究2015

    • Author(s)
      ○南川亮、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス/薬学部 (千葉県船橋市)
    • Year and Date
      2015-03-26
    • Related Report
      2014 Annual Research Report
  • [Presentation] (-)-Stemonineの合成研究2015

    • Author(s)
      ○寄立麻琴、高橋芳人、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス/薬学部 (千葉県船橋市)
    • Year and Date
      2015-03-26
    • Related Report
      2014 Annual Research Report
  • [Presentation] Total Synthesis of Sphingofungin F2014

    • Author(s)
      Takaaki Sato
    • Organizer
      Vietnam Malaysian International Chemical Congress
    • Place of Presentation
      Hanoi (Vietnam)
    • Year and Date
      2014-11-07
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] マダンガミン類の合成研究2014

    • Author(s)
      ○柳田悠太、松尾直哉、黒須靖弘、須藤貴弘、佐藤隆章、千田憲孝
    • Organizer
      第106回有機合成シンポジウム
    • Place of Presentation
      早稲田大学 国際会議場 (東京都新宿区)
    • Year and Date
      2014-11-07
    • Related Report
      2014 Annual Research Report
  • [Presentation] Total Synthesis of Gephyrotoxin by Amide-Selective Nucleophilic Addition2014

    • Author(s)
      Takaaki Sato
    • Organizer
      18th Malaysian International Chemical Congress
    • Place of Presentation
      Kuala Lumpur (Malaysia)
    • Year and Date
      2014-11-03
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Chemoselective Nucleophilic Addition to N-Alkoxyamides: Development and Application to the Total Synthesis of Gephyrotoxin2014

    • Author(s)
      Takaaki Sato
    • Organizer
      3rd International Conference on Organic Chemistry
    • Place of Presentation
      Tbilisi (Georgia)
    • Year and Date
      2014-09-26
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Copper-Catalyzed Electrophilic Amination of N-Methoxyamines2014

    • Author(s)
      ○Takaaki Sato, Takamasa Wada, Yutaro Fukami, Noritaka Chida
    • Organizer
      13th International Conference of Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌 (北海道札幌市)
    • Year and Date
      2014-07-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] アミド基への求核付加反応から始まる天然物全合成2014

    • Author(s)
      佐藤隆章
    • Organizer
      第49回天然物化学談話会
    • Place of Presentation
      せとうち児島ホテル (岡山県倉敷市)
    • Year and Date
      2014-07-03
    • Related Report
      2014 Annual Research Report
  • [Presentation] 多置換N-メトキシアミンの二段階合成法の開発2014

    • Author(s)
      ○寄立麻琴、目黒達彦、松尾直哉、白兼研史、佐藤隆章、千田憲孝
    • Organizer
      第105回 有機合成化学シンポジウム
    • Place of Presentation
      東京工業大学大岡山キャンパス (東京都目黒区)
    • Year and Date
      2014-06-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] N-メトキシアミノ基を用いた三成分反応の開発とLasubineⅡの全合成2014

    • Author(s)
      ○横山貴,深見祐太朗,黒崎友介,白兼研史,佐藤隆章,千田憲孝
    • Organizer
      有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      慶應義塾大学矢上キャンパス (神奈川県横浜市)
    • Year and Date
      2014-05-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] ゲフィロトキシンの全合成:官能基選択的なアミド基への求核付加反応の開発と応用

    • Author(s)
      ○佐藤隆章、白兼研史、和田崇正、寄立真琴、南川亮、高山展明、千田憲孝
    • Organizer
      第103回有機合成シンポジウム
    • Place of Presentation
      慶應義塾大学薬学部
    • Related Report
      2013 Research-status Report
  • [Presentation] 官能基選択的なアミド基への求核付加反応の開発と天然物全合成への応用

    • Author(s)
      ○佐藤隆章
    • Organizer
      第48回天然物化学談話会
    • Place of Presentation
      滋賀県大津市
    • Related Report
      2013 Research-status Report
  • [Presentation] Gephyrotoxinの全合成:N-メトキシアミドに対する官能基選択的な求核付加反応の開発と応用

    • Author(s)
      佐藤隆章、○白兼研史、和田崇正、寄立麻琴、南川亮、高山展明、千田憲孝
    • Organizer
      第55回天然有機化合物討論会
    • Place of Presentation
      同志社大学寒梅館
    • Related Report
      2013 Research-status Report
  • [Presentation] ゲフィロトキシンの全合成:官能基選択的なアミド基への求核付加反応の開発と応用

    • Author(s)
      ○佐藤隆章、白兼研史、和田崇正、寄立麻琴、南川亮、高山展明、千田憲孝
    • Organizer
      第43回複素環化学討論会
    • Place of Presentation
      滋賀県岐阜市
    • Related Report
      2013 Research-status Report
  • [Presentation] 多置換N-メトキシアミンの二段階合成法

    • Author(s)
      ○寄立麻琴、目黒達彦、松尾直哉、白兼研史、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
  • [Presentation] ゲフィロトキシンの改良全合成

    • Author(s)
      ○白兼研史、和田崇正、寄立麻琴、南川亮、高山展明、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
  • [Presentation] 銅触媒を用いたN-アルコキシアミンの求電子的アミノ化反応

    • Author(s)
      ○和田崇正、深見祐太朗、佐藤隆章、千田憲孝
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
  • [Presentation] Total Synthesis of Gephyrotoxin: Development and Application of Chemoselective Nucleophilic Addition to Amides

    • Author(s)
      Takaaki Sato
    • Organizer
      15th Asian Chemical Congress
    • Place of Presentation
      Singapore
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Total Synthesis of Gephyrotoxin via Amide-Selective Nucleophilic Addition

    • Author(s)
      Takaaki Sato
    • Organizer
      The Overman Symposium
    • Place of Presentation
      USA (Indianapolis)
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] 不活性アミド基に対する連続的な求核付加反応

    • Author(s)
      佐藤隆章
    • Organizer
      第101回 有機合成シンポジウム
    • Place of Presentation
      慶應義塾大学薬学部
    • Related Report
      2012 Research-status Report
  • [Presentation] アルコキシアミド基に対する 直接的な求核付加反応

    • Author(s)
      佐藤隆章
    • Organizer
      第42回 複素環化学討論会
    • Place of Presentation
      京都テルサ
    • Related Report
      2012 Research-status Report
  • [Presentation] Direct Nucleophilic Addition to N-Alkoxyamides

    • Author(s)
      佐藤隆章
    • Organizer
      17th Malaysian Chemical Congress
    • Place of Presentation
      クアラルンプール、マレーシア
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] Direct Nucleophilic Addition to N-Alkoxyamides

    • Author(s)
      佐藤隆章
    • Organizer
      Cambodian Malaysian Chemical Conference
    • Place of Presentation
      シェムリアップ、カンボジア
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] Direct Nucleophilic Addition to N-Alkoxyamides

    • Author(s)
      佐藤隆章
    • Organizer
      The 11th International Symposium on Advanced Technology
    • Place of Presentation
      工学院大学
    • Related Report
      2012 Research-status Report
  • [Presentation] N -メトキシアミンを用いた 三成分反応の開発と応用

    • Author(s)
      深見祐太朗
    • Organizer
      日本化学会第 93春季年会
    • Place of Presentation
      立命館大学 びわこ・くさつキャンパス
    • Related Report
      2012 Research-status Report
  • [Presentation] 連続的Overman/Claisen転位を鍵とした (–)-Stemoamideの全合成

    • Author(s)
      中山泰彰
    • Organizer
      日本化学会第 93春季年会
    • Place of Presentation
      立命館大学 びわこ・くさつキャンパス
    • Related Report
      2012 Research-status Report
  • [Presentation] Gephyrotoxinの全合成:N-メトキシアミドに対する官能基選択的な求核付加反応の開発と応用

    • Author(s)
      白兼研史
    • Organizer
      日本化学会第 93春季年会
    • Place of Presentation
      立命館大学 びわこ・くさつキャンパス
    • Related Report
      2012 Research-status Report
  • [Book] Comprehensive Chirality2012

    • Author(s)
      千田憲孝
    • Publisher
      Elsevier Science
    • Related Report
      2012 Research-status Report
  • [Remarks] 千田研究室ホームページ

    • URL

      http://www.applc.keio.ac.jp/~chida/

    • Related Report
      2012 Research-status Report

URL: 

Published: 2013-05-31   Modified: 2019-07-29  

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